JPH026525A - Glass-reinforced polymer molding and its production - Google Patents
Glass-reinforced polymer molding and its productionInfo
- Publication number
- JPH026525A JPH026525A JP15672988A JP15672988A JPH026525A JP H026525 A JPH026525 A JP H026525A JP 15672988 A JP15672988 A JP 15672988A JP 15672988 A JP15672988 A JP 15672988A JP H026525 A JPH026525 A JP H026525A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- metathesis
- silane coupling
- coupling agent
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000465 moulding Methods 0.000 title claims abstract description 25
- 229920000642 polymer Polymers 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000011521 glass Substances 0.000 claims abstract description 76
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 52
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 19
- 230000002787 reinforcement Effects 0.000 claims abstract description 15
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 9
- 239000012779 reinforcing material Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 36
- 239000002131 composite material Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 23
- 229910000077 silane Inorganic materials 0.000 abstract description 22
- 239000004593 Epoxy Substances 0.000 abstract description 9
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 abstract description 8
- 239000004744 fabric Substances 0.000 abstract description 4
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 abstract description 2
- 229910003091 WCl6 Inorganic materials 0.000 abstract 1
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 abstract 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- 239000003365 glass fiber Substances 0.000 description 16
- 239000000178 monomer Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
- -1 cyclic olefins Chemical class 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000005452 bending Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 239000000835 fiber Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 8
- 229910052721 tungsten Inorganic materials 0.000 description 8
- 239000010937 tungsten Substances 0.000 description 8
- 239000002759 woven fabric Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000003658 tungsten compounds Chemical class 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920006037 cross link polymer Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920006112 polar polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- POPHMOPNVVKGRW-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7-octahydronaphthalene Chemical compound C1CCC2CCCCC2=C1 POPHMOPNVVKGRW-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- RXNOYRCWKRFNIM-UHFFFAOYSA-N 2-carbonochloridoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(Cl)=O RXNOYRCWKRFNIM-UHFFFAOYSA-N 0.000 description 1
- PNRZRBBBDPNPQM-UHFFFAOYSA-N 2-ethylhexyl 5-methylbicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OCC(CC)CCCC)(C)CC1C=C2 PNRZRBBBDPNPQM-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- KXYDGGNWZUHESZ-UHFFFAOYSA-N 4-(2,2,4-trimethyl-3h-chromen-4-yl)phenol Chemical compound C12=CC=CC=C2OC(C)(C)CC1(C)C1=CC=C(O)C=C1 KXYDGGNWZUHESZ-UHFFFAOYSA-N 0.000 description 1
- YKZUNWLMLRCVCW-UHFFFAOYSA-N 4-[2-(4-bicyclo[2.2.1]hept-2-enyl)ethyl]bicyclo[2.2.1]hept-2-ene Chemical compound C1CC(C2)C=CC21CCC1(C=C2)CC2CC1 YKZUNWLMLRCVCW-UHFFFAOYSA-N 0.000 description 1
- JGLIHSMBVDZMSA-UHFFFAOYSA-N 5-(cyclohexen-1-yl)bicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CCCCC1 JGLIHSMBVDZMSA-UHFFFAOYSA-N 0.000 description 1
- OWETXGRKCLKMMD-UHFFFAOYSA-N 5-(phenoxymethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CC2C1COC1=CC=CC=C1 OWETXGRKCLKMMD-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-UHFFFAOYSA-N 5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=CC)CC1C=C2 OJOWICOBYCXEKR-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- BMAXQTDMWYDIJX-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carbonitrile Chemical compound C1C2C(C#N)CC1C=C2 BMAXQTDMWYDIJX-UHFFFAOYSA-N 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- BWKCCRPHMILRGD-UHFFFAOYSA-N chloro hypochlorite;tungsten Chemical compound [W].ClOCl BWKCCRPHMILRGD-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- NOSWQDCFTDHNCM-UHFFFAOYSA-N cyclopenta-1,3-diene;1-methylcyclopenta-1,3-diene Chemical compound C1C=CC=C1.CC1=CC=CC1 NOSWQDCFTDHNCM-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 206010073071 hepatocellular carcinoma Diseases 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- AGQPHHBPENBBIO-UHFFFAOYSA-M iodo(dioctyl)alumane Chemical compound [I-].CCCCCCCC[Al+]CCCCCCCC AGQPHHBPENBBIO-UHFFFAOYSA-M 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- KUVXJBSVPBXHEK-UHFFFAOYSA-N octylaluminum Chemical compound CCCCCCCC[Al] KUVXJBSVPBXHEK-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
ａ、産業上の利用分野
本発明は、メタセシス重合性シクロオレフィンモノマー
をメタセシス重合触媒の存在下で、重合と同時に成型を
おこなって得られる重合体成型物であってそのガラス強
化成型物に関するものである。Detailed Description of the Invention a. Industrial Application Field The present invention is a polymer molded product obtained by simultaneously polymerizing and molding a metathesis-polymerizable cycloolefin monomer in the presence of a metathesis polymerization catalyst. This relates to glass-reinforced molded products.
さらに詳しくは、特定のシランカップリング剤でシラン
処理をしたガラス補強材を用いて、メタセシス重合体と
の接着性を改善したガラス強化重合体成型物及びその製
造方法に関するものである。More specifically, the present invention relates to a glass-reinforced polymer molded product that has improved adhesion to a metathesis polymer by using a glass reinforcing material that has been silane-treated with a specific silane coupling agent, and a method for producing the same.
ｂ、従来技術
環状オレフィンがメタセシス重合触媒系によって開環重
合体を与えることは公知である。そこでジシクロペンタ
ジェン（ＤＣＰ）の如く安価に得られるメタセンス重合
性環状オレフィンをメタセシス重合触媒系によって鋳型
内で重合と成型を一段階でおこなって重合成型物を得る
方法が提案された。すなわち、メタセシス重合触媒系が
、塩化タングステンの如き触媒成分と、アルキルアルミ
ニウムの如き、活性止剤成分との二成分よりなることを
利用し、各二成分とモノマーとからなる二種類の液を用
いて重合時に急速混合の後鋳型内に流し込み重合体成型
物を得る方法が提案された（例えば、特開昭５８−１２
９０１３号公報参照）。b. Prior Art It is known that cyclic olefins can be subjected to metathesis polymerization catalyst systems to give ring-opened polymers. Therefore, a method has been proposed in which a metasense polymerizable cyclic olefin, such as dicyclopentadiene (DCP), which can be obtained at low cost, is polymerized and molded in a mold in one step using a metathesis polymerization catalyst system to obtain a polymerized molded product. That is, by taking advantage of the fact that the metathesis polymerization catalyst system consists of two components: a catalyst component such as tungsten chloride and an activation inhibitor component such as alkyl aluminum, two types of liquids consisting of each of the two components and a monomer are used. A method was proposed in which a polymer molded product was obtained by rapidly mixing during polymerization and then pouring it into a mold (for example, in JP-A-58-12
(See Publication No. 9013).
かかる方法によれば安価な低圧鋳型を用いて、大型成型
物が１ｑられる。かつ、かかる成型物は、剛性と１ｆｆ
１衝撃性の良好なバランスを有しており工業的に非常に
魅力ある方法といえる。According to this method, a large molded product of 1 q can be made using an inexpensive low-pressure mold. And, such a molded product has rigidity and 1ff
1) It has a good balance of impact resistance and can be said to be a very attractive method industrially.
しかしながら用途によっては、より高い剛性とより高い
寸法安定性と、ざらに改良された熱変形温度が要求され
る場合も多いことが判ってきた。However, it has been found that certain applications often require higher stiffness, higher dimensional stability, and significantly improved heat distortion temperatures.
かかる成型物として重要な三つの性能向上を同時に達成
しうるための解決方策として補強材を用いること、それ
も、特に安価で有効なガラス補強材を用いる方法をあげ
ることができる。ところで、ガラス補強材がその特性を
充分発揮しうるためには、樹脂と補強材とがその界面に
おいてよく接着していることが必要である。しかし一般
に極性の大きいガラス表面と各種の樹脂の表面エネルギ
は、相違していることは多く、良好な接着性を得るため
に、シランカップリング剤を用いる方法が一般に用いら
れている。かかるシランカップリング剤はシラノール系
の基を通じてカラスとの接着性に寄与する部分と、用い
られる樹脂と強い相互作用を有する有１１基の部分の両
方を有する化合物で、既に何種かのものが市販され、ポ
リアミド樹脂、ポリエステル樹脂、エポキシ樹脂、フェ
ノル樹脂等ガラス強化によく用いられる熱硬化性樹脂、
熱可塑性樹脂の各々に適したシランカップリング剤が選
択できるようになっている。A solution to simultaneously achieving three important performance improvements for such molded products is to use a reinforcing material, and in particular, a method using a glass reinforcing material, which is inexpensive and effective, can be mentioned. By the way, in order for the glass reinforcing material to fully exhibit its properties, it is necessary that the resin and the reinforcing material are well bonded at the interface. However, the surface energies of glass surfaces, which are generally highly polar, and various resins are often different, and in order to obtain good adhesion, a method using a silane coupling agent is generally used. Such silane coupling agents are compounds that have both a moiety that contributes to adhesion to glass through a silanol group and a moiety that has 11 groups that have a strong interaction with the resin used, and several types have already been developed. Thermosetting resins that are commercially available and often used for glass reinforcement, such as polyamide resins, polyester resins, epoxy resins, and phenolic resins,
Silane coupling agents suitable for each thermoplastic resin can be selected.
しかしながら、上述した如きメタセシス重合性シクロオ
レフィンのメタセシス重合触媒による重合と成型を同時
におこなって得られる重合体成型物に用いられるガラス
補強材の接着性向上に寄与しうるシランカップリング剤
として如何なるものが効果をもらうるかについては全く
知られていない。かつ、かかる重合体成型物は重合と同
時に成型をおこなうことを特徴としているため、ガラス
補強材は、メタセシス重合中に既に系内に存在し、反応
剤とその表面は接触していることになり、従って、かか
るカップリング剤がメタセシス重合を阻害するものであ
ってはならないことになるが、かかるシランカップリン
グ剤のその挙動についても知られていない。However, what kind of silane coupling agent is available that can contribute to improving the adhesion of a glass reinforcing material used in a polymer molded product obtained by simultaneously polymerizing and molding a metathesis-polymerizable cycloolefin using a metathesis polymerization catalyst as described above? Nothing is known about its effectiveness. Moreover, since such polymer molded products are characterized by being molded simultaneously with polymerization, the glass reinforcing material is already present in the system during metathesis polymerization, and the reactant and its surface are in contact with each other. Therefore, it follows that such coupling agents should not inhibit metathesis polymerization, but the behavior of such silane coupling agents is also unknown.
ざらに、上述の如きメタセシス重合体は一般に不飽和結
合を多く有する炭化水素構造を有することになるが、成
型後、空気と接触する面は、すみやかに酸化され極性基
が導入され、表面の性質は大巾にかわり、極性の接着剤
や塗料との接着性は良好となるが、生成直撲は極性がな
く、表面エネルギーが小さい可能性があるが、ガラス補
強材はその生成中あるいは生成した直後の樹脂と接着す
ることになる訳である。In general, metathesis polymers such as those mentioned above generally have a hydrocarbon structure with many unsaturated bonds, but after molding, the surface that comes into contact with air is quickly oxidized and polar groups are introduced, resulting in changes in surface properties. The material has a strong adhesive property and has good adhesion with polar adhesives and paints, but the surface energy of the directly formed material is non-polar and may have small surface energy, but the glass reinforcement material is This means that it will be bonded to the resin immediately after.
以上、メタセシス重合体に適したシランカップリング剤
については、全く知られておらず、かつ、その選定には
多くの困難が予測されるが、良好なガラス補強重合体成
型物を得るためにはその選定が不可欠となる。As mentioned above, nothing is known about silane coupling agents suitable for metathesis polymers, and many difficulties are expected in their selection, but in order to obtain good glass-reinforced polymer moldings, Its selection is essential.
そこで本発明者は、メタセシス重合体成型物用ガラス補
強材用のシランカップリング剤を見出すべく鋭意検討の
結果、比較的一般に用いられているシランカップリング
剤中に優れた機能を発揮するシランカップリング剤があ
ることを見出し得て本発明に到達したものである。Therefore, as a result of intensive studies to find a silane coupling agent for glass reinforcing materials for metathesis polymer moldings, the present inventor found a silane coupling agent that exhibits excellent functionality among the relatively commonly used silane coupling agents. The present invention was achieved by discovering that there is a ring agent.
Ｃ０発明の構成
即ち、本発明者は、シランカップリング剤のメタセシス
重合に対する影響をみるには、各々のシランカップリン
グ剤で処理したガラス板の存在下にメタセシス重合性を
おこなわせ重合の進行速度の変化を比較する方法等を、
またメタセシス重合体とガラスの接着性の改善の状態を
定性的にスクリーニングする方法としては、各々のシラ
ンカップリング剤で処理したガラス板上で、メタセシス
重合性モノマーをメタセシス重合触媒によって重合せし
め、生じた樹脂とガラス板との接着を比較する方法を案
出することによって、シランカップリング剤のメタセシ
ス重合体との適合性をテストした。Structure of the C0 Invention: In order to examine the influence of silane coupling agents on metathesis polymerization, the inventor conducted metathesis polymerization in the presence of a glass plate treated with each silane coupling agent, and determined the rate of progress of polymerization. How to compare changes in
In addition, as a method for qualitatively screening the state of improvement in adhesion between metathesis polymers and glass, a metathesis polymerizable monomer is polymerized with a metathesis polymerization catalyst on a glass plate treated with each silane coupling agent, and the resulting We tested the compatibility of silane coupling agents with metathesis polymers by devising a method to compare the adhesion between the resin and the glass plate.
ざらにより直接的に、その効果を見る方法としてシラン
カップリング剤以外の紡糸油剤等の影響を容易に排除し
た］ナンプルが得られるガラス織布に看目し、バーニン
グ処理をして表面をきれいにしたガラス織布に、各々の
各種シランカップリング剤で処理し、そのシラン処理ガ
ラス織布を強化材として用いて、ガラス繊維メタセシス
重合体コンポジットを作成し、ガラスと樹脂のぬれ、接
着の状況が最もよく表われる曲げ強度２曲げモジュラス
を測定し比較する方法を重ねることにした。As a way to directly see the effect of roughness, the influence of spinning oils other than silane coupling agents was easily eliminated.] Looking at the glass woven fabric from which the sample was obtained, we performed a burning process to clean the surface. Glass woven fabric is treated with various silane coupling agents, and the silane-treated glass woven fabric is used as a reinforcing material to create a glass fiber metathesis polymer composite. We decided to overlap the methods of measuring and comparing bending strength and bending modulus, which are commonly expressed.
その結果、エポキシシラン系シランカップリング剤がメ
タセシス重合体用ガラス補強材に用いるシランカップリ
ング剤として非常に優れた特性を有することを見出し得
たもので必る。As a result, it has been found that epoxysilane-based silane coupling agents have very excellent properties as silane coupling agents for use in glass reinforcing materials for metathesis polymers.
即ら、本発明は下記発明を包含する。That is, the present invention includes the following inventions.
（１）エポキシシラン系シランカップリング剤で処理し
たガラス補強材と、少なくとも１種のメタレタス重合性
シクロオレフィンをメタセンス重合触媒系によって重合
と成型を同時におこなって得られる重合体とより少なく
ともなるガラス強化重合体成型物。(1) Glass reinforcement made of at least a glass reinforcing material treated with an epoxysilane-based silane coupling agent and a polymer obtained by simultaneously polymerizing and molding at least one type of metaletas polymerizable cycloolefin using a metasense polymerization catalyst system. Polymer molding.
（２）メタセシス重合性シクロオレフィンの少なくとも
１種を、エポキシシラン系シランカップリング剤で処理
したガラス補強材の共存下、メタセンス重合触媒系によ
って重合と成型を同時におこなうことを特徴とするガラ
ス強化重合体成型物の製造方法。(2) A glass-reinforced polymer characterized in that polymerization and molding of at least one metathesis-polymerizable cycloolefin are simultaneously performed using a metasense polymerization catalyst system in the coexistence of a glass reinforcing material treated with an epoxysilane-based silane coupling agent. A method for manufacturing a composite molded product.
エポキシシラン系シラン処理剤は一般に下記−般式（Ｉ
）で表わされる。The epoxy silane-based silane treatment agent generally has the following general formula (I
).
但し、式中Ｒは１価のアルキル基、Ｒは２〜３価のアル
キレン基（但しＲ，Ｒ’ ともにエーテルやエステル等
の極性基を含有していても差支えない）。ｍは１〜３の
整数である。・・・は、なし又は１かの原子価を表わす
。ガラス表面との親和性の見地から待にｍ＝２．３が好
ましく特にｍ＝３の場合が好ましい。However, in the formula, R is a monovalent alkyl group, and R is a divalent to trivalent alkylene group (however, both R and R' may contain polar groups such as ether or ester). m is an integer from 1 to 3. ... represents a valence of none or 1. From the viewpoint of affinity with the glass surface, m=2.3 is particularly preferred, and m=3 is particularly preferred.
Ｒはかかるシランカップリング剤がガラスと接合する場
合には加水分解して、カップリング状態では残らない基
であり、従って、シランカップリング剤のガラス補強材
への処理条件によって適当なものが選択されればよい。R is a group that is hydrolyzed when the silane coupling agent is bonded to glass and does not remain in the coupled state. Therefore, an appropriate one is selected depending on the processing conditions of the silane coupling agent to the glass reinforcing material. It is fine if it is done.
即ら、シランカップリング剤の適用は前もってシランカ
ップリング剤で処理したガラス補強材を用いる方法と、
逆にシランカップリング剤を、重合性の溶液中に添加し
てあき硬化と同時にガラス補強材へのシラン処理も同時
に行う方法との２法がある。That is, the application of a silane coupling agent involves using a glass reinforcement material that has been previously treated with a silane coupling agent;
On the other hand, there are two methods: a method in which a silane coupling agent is added to a polymerizable solution and the glass reinforcing material is simultaneously treated with silane at the same time as hardening.
後者の方法は、ガラス補強材へのシラン処理の工程を省
略できる長所があるが、ガラス補強材へのシラン処理は
、重合性の溶液との接触も同時に起り、かつ、重合条件
中にシラン処理もおこなわれねばならないことになり、
シランカップリング剤は、理論必要量よりもかなり多量
に添加される必要があり、かつ、このように添加された
シランカップリング剤は重合反応に影響がないことが要
求されるばかりでなく、シラン処理剤の分解によって生
じたヒドロキシル基を有するＲＯＨにあたる化合物がざ
らに重合反応及び生じた重合体に悪影響をうけないこと
になり、かつ、重合体の表面にも存在しうるシラン残基
が重合体成型物の以後の加工、例えば塗装等に悪影響を
与えないこと等の条件が要求され、その要求に適したＲ
か選択されることになる。本発明のメタセシス重合体の
場合は前述の如く、メタセシス重合反応が極性化合物の
共存に敏感であり、かつ、重合の進行が早いので、シラ
ン処理との同時進行に困難がともない、前者の方法の適
用が好ましい。The latter method has the advantage of omitting the step of silane treatment of the glass reinforcement material, but silane treatment of the glass reinforcement material also involves contact with the polymerizable solution at the same time, and the silane treatment is not performed during the polymerization conditions. It will also be necessary to carry out
The silane coupling agent needs to be added in a much larger amount than the theoretically required amount, and the silane coupling agent added in this way is not only required to have no effect on the polymerization reaction, but also to The ROH compound having a hydroxyl group generated by the decomposition of the treatment agent will not be adversely affected by the polymerization reaction and the resulting polymer, and the silane residues that may be present on the surface of the polymer will be removed. Conditions such as not having an adverse effect on the subsequent processing of the molded product, such as painting, are required, and R is suitable for those requirements.
or will be selected. In the case of the metathesis polymer of the present invention, as mentioned above, the metathesis polymerization reaction is sensitive to the coexistence of polar compounds and the polymerization progresses quickly, so it is difficult to proceed simultaneously with silane treatment, and the former method is difficult. Application is preferred.
前者の場合は、ガラス補強材のシラン処理の際に一般に
溶媒を用いて希釈したシランカップリング剤をガラス補
強材に接触させ、乾燥、熱処理によって、シランカップ
リング剤をガラス補強材表面に固着させることになる。In the former case, during the silane treatment of the glass reinforcing material, a silane coupling agent diluted with a solvent is generally brought into contact with the glass reinforcing material, and the silane coupling agent is fixed to the surface of the glass reinforcing material by drying and heat treatment. It turns out.
かかる溶剤としては工業的見地では水が最も好ましく、
次いで、水とアルコールやアセトン等の極性有機溶媒と
の混合物が用いられることになり、それとの混和性と、
処理速度等の面で適当なものが選ばれることになるが、
一般に低級アルキル基例えば、メチル、エチル、メトキ
シエチル等の基が用いられるが特にメチル基が一般的で
あり好ましい。Water is the most preferred solvent from an industrial standpoint;
Next, a mixture of water and a polar organic solvent such as alcohol or acetone will be used, and its miscibility and
An appropriate one will be selected in terms of processing speed, etc.
Lower alkyl groups such as methyl, ethyl, and methoxyethyl are generally used, with methyl being particularly common and preferred.
好適なエポキシシラン系シランカップリング剤としでは
次の如きものをめげることができる。Suitable epoxysilane-based silane coupling agents include the following.
γ−グリシドキシプロピル１〜リメＩ〜キシシラン（Ｉ
−ａ）
γ−グリシドキシプロビルメチルジメトキシシラン
（Ｉ −ｂ）β−（３，４−
エポキシシクロヘキシル）エチルトリメ１へキシシラン
（Ｉ−Ｃ）かかるエポキシシラン類が、
メタセシス重合体に対し良好な接着性を示す理由は明確
ではない。γ-glycidoxypropyl 1-lime I-xysilane (I
-a) γ-glycidoxypropylmethyldimethoxysilane
(I-b)β-(3,4-
Epoxycyclohexyl)ethyltrimethylhexysilane (I-C) Such epoxysilanes are
The reason for the good adhesion to metathesis polymers is not clear.
エポキシ基は一般には、メタセシス重合触媒に対する阻
害性化合物であることが判っている所から、かかるエポ
キシシラン類か良好な接着性を示すのは意外な知見であ
った。メタセシス重合触媒系は、カチオン重合触媒とし
ての作用もあることか予測される所から、その作用によ
って、エポキシ基の開環重合が起りこれらが、メタセシ
ス重合体と結合するか強い相互作用を発揮するためとも
考えられる。Since epoxy groups are generally known to be compounds that inhibit metathesis polymerization catalysts, it was a surprising finding that such epoxy silanes exhibited good adhesive properties. Since it is predicted that the metathesis polymerization catalyst system also acts as a cationic polymerization catalyst, ring-opening polymerization of epoxy groups occurs due to this action, and these bond with the metathesis polymer or exhibit a strong interaction. It is also possible that this is due to the reason.
本発明で用いられるガラス補強材は、繊維状。The glass reinforcing material used in the present invention is fibrous.
粉末状等いかなるものも用いることができる。Any material such as powder can be used.
ガラス繊維補強材としては、ガラス長繊維を織ったガラ
ス織布、ガラス長繊維の繊維ストランドをランダムコイ
ル状に平面に広げてバインダーで固定したコンティニュ
アス・ガラスストランドマット、カットした繊維ストラ
ンドを表面上にランダムにからみあわせバインダーで固
定したチョツプド・ストランドマツ１〜、該チョップト
ス１ヘランドをおる立体的な形に吹きつけバインダーで
固定したチョツプドストランドプリフォーム、ガラス繊
維を通常の不織１５を作る方法と同じ方法、例えばニー
ドルパンチ法を適用したガラス繊維、不織布、ガラス繊
維トウを一方向に平行に引揃え平面に並べ、他種のマッ
トに張り合わけるか、横方向をステイフナでとめた、一
方向性平行布等をあげることができる。Glass fiber reinforcement materials include glass woven cloth made from long glass fibers, continuous glass strand mats made by spreading fiber strands of long glass fibers into a random coil shape and fixing them with a binder, and cutting fiber strands on the surface. Chopped strand pine 1 ~ randomly intertwined and fixed with a binder on top, chopped strand preform blown into a three-dimensional shape and fixed with a binder over the chop toss 1 herand, and ordinary non-woven glass fiber 15 Glass fibers, non-woven fabrics, and glass fiber tows are lined up in parallel in one direction on a plane using the same method as the needle punching method, and either they are pasted onto other types of mats, or they are fastened in the horizontal direction with stiffeners. Examples include unidirectional parallel cloth.
また、繊維以外の形態のものとしては、ガラスを粉末状
にくだいたミルドガラス、粉末状ではあるが大きなアス
ペクト比をもったいわゆるマイクロ・ファイバー状ガラ
ス、ガラスマイクロバルーン、リン片状ガラス等をめげ
ることができる。In addition, forms other than fibers include milled glass, which is glass broken into powder, so-called micro-fiber glass, which is powdered but has a large aspect ratio, glass microballoons, flaky glass, etc. be able to.
本発明において、メタセシス重合体の補強用として用い
る場合、前者のガラス繊維系のものと後者の粉末状ガラ
ス補強材は、一般にその適用方法が異なり、使用効果に
ついても異なる。In the present invention, when used for reinforcing a metathesis polymer, the former glass fiber-based reinforcing material and the latter powdered glass reinforcing material generally have different application methods and different usage effects.
即ら、ガラス繊維系補強材は、一般に、成型金型内に予
め、マットやプリフォーム状のものを配置しておき、そ
こへ反応性の七ツマー液を注入する方法がとられる。か
かる方法においてはモノマー液がガラス繊維束内に出来
るだけ空隙をつくらないよう、充分に繊維束中に浸透し
て固化する必要があり、成型上の難しさが増しかつ成型
速度も遅くなることが多い。しかしそれが出来ればその
補強効果は大きく、剛性１強度２寸法安定性、熱変形温
度の向上ばかりでなく、例えばノツチ付アイゾツトで代
表される耐衝撃強度も大巾に向上する。That is, the glass fiber reinforcing material is generally prepared in the form of a mat or preform in advance in a molding die, and a reactive 7-mer solution is injected therein. In such a method, it is necessary for the monomer liquid to sufficiently penetrate into the fiber bundle and solidify so as to minimize the creation of voids within the glass fiber bundle, which increases the difficulty in molding and slows down the molding speed. many. However, if this can be done, the reinforcing effect will be great, and not only will the rigidity, strength, and dimensional stability and thermal deformation temperature be improved, but also the impact strength, as typified by notched isots, will be greatly improved.
一方、粉末状のガラス補強材の場合は、反応性モノマー
液に予め分散したものを金型内に注入する方法が用いら
れる。分散液の安定性や、反応射出成型の場合、射出ノ
ズルの摩耗やつまり等の問題はあるが、原則的には、補
強材のないものと同様に成型が可能である利点は有して
いるが、ガラス繊維に比して、アスペクト比が小さくな
るため、剛性１強度１寸法安定性、熱変形温度の向上の
程度が同じガラス含有率でも、大きく劣ってしまい、か
つ、ノツチ付アイゾツ１〜耐衝撃強度は、補強材−樹脂
間のマイクロクラックのため一般に低下する等補強効果
が限られてくることになる。On the other hand, in the case of a powdered glass reinforcing material, a method is used in which the reinforcing material is pre-dispersed in a reactive monomer liquid and injected into a mold. Although there are problems with the stability of the dispersion and the wear and clogging of the injection nozzle in the case of reaction injection molding, in principle it has the advantage that it can be molded in the same way as without reinforcing material. However, since the aspect ratio is smaller than that of glass fiber, even if the glass content has the same degree of improvement in rigidity, strength, dimensional stability, and heat distortion temperature, it is significantly inferior to notched Izotsu 1~ The impact resistance strength generally decreases due to microcracks between the reinforcing material and the resin, which limits the reinforcing effect.
ガラス補強材へのエポキシシラン系シランカップリング
剤への適用処理は前記の如く、一般のシランカップリン
グ剤をガラス補強材へ適用する方法として確立している
方法をそのまま用いることができる。特にチョツプドあ
るいはコンテイニュアスストランドを基材とするカラス
繊維補強材の場合は、紡糸の際の油剤の一成分にシラン
カップリング剤を加えておき、紡糸工程中の同時にシラ
ンカップリング剤を付着させてしまう方法をとることも
できる。As described above, the process of applying the epoxysilane-based silane coupling agent to the glass reinforcing material can be carried out using the method that has been established as a method for applying a general silane coupling agent to the glass reinforcing material. In particular, in the case of glass fiber reinforcement materials based on chopped or continuous strands, a silane coupling agent is added to one of the oil components during spinning, and the silane coupling agent is attached at the same time during the spinning process. You can also take a method of letting it happen.
本発明に用いられるメタセシス重合性シクロオレフィン
モノマーの好適な具体例としては、ジシクロペンタジェ
ン、トリシクロペンタジェン、シクロペンタジェン−メ
チルシクロペンタジェン共二量体、５−エチリデンノル
ボルネン、ノルボルネン、ノルボルナジェン、５−シク
ロへキセニルノルボルネン、１・、４，５．８−ジメタ
ノ−１，４，４ａ、 ５．６、７．８．８．８ａ−オク
タヒドロナフタレン、１，４−メタノ−１，４，４ａ、
５，８．７，８，８．８ａ−オクタヒドロナフタレン、
６−エチリデン−１，４，５，８−ジメタノ−１、４，
４ａ、 ５．６．７．８．８ａ−へブタヒドロ−ナフタ
レン。Preferred specific examples of the metathesis-polymerizable cycloolefin monomer used in the present invention include dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene codimer, 5-ethylidenenorbornene, norbornene, norbornadiene. , 5-cyclohexenylnorbornene, 1., 4,5.8-dimethano-1,4,4a, 5.6, 7.8.8.8a-octahydronaphthalene, 1,4-methano-1, 4,4a,
5,8.7,8,8.8a-octahydronaphthalene,
6-ethylidene-1,4,5,8-dimethano-1,4,
4a, 5.6.7.8.8a-hebutahydro-naphthalene.
６−メチル−１，４，５，８−ジメタノ−１，４，４ａ
、５，６，７．８．８ａ−へブタヒドロナフタレン、
１，４，５．８−ジメタノ−１，４，４ａ、 ５，８．
８ａ−へキサヒドロナフタレン、エチレンビス（５−ノ
ルボルネン）などの１〜３個のノルボルネン構造を有す
る環状オレフィンの一種または二種以上の混合物をあげ
ることができるが特にジシクロペンタジェン又は、それ
を主体とする七ツマー混合物が好適に用いられる。6-methyl-1,4,5,8-dimethano-1,4,4a
, 5,6,7.8.8a-hebutahydronaphthalene,
1,4,5.8-dimethano-1,4,4a, 5,8.
Examples include one or a mixture of two or more cyclic olefins having 1 to 3 norbornene structures such as 8a-hexahydronaphthalene and ethylenebis(5-norbornene), but dicyclopentadiene or a mixture thereof can be mentioned. A mixture consisting mainly of hepatoma is preferably used.
また、必要に応じて、酸素、窒素等の異種元素を有する
メタセシス重合ｌ環状化合物を用いることもできる。か
かる極性上ツマー類は、ジシクロペンタジェン等との共
重合で用いられることが多い。Further, if necessary, a metathesis-polymerized l-cyclic compound containing a different element such as oxygen or nitrogen can also be used. Such polar polymers are often used in copolymerization with dicyclopentadiene and the like.
かかる極性上ツマ−も、ノルボルネン構造単位を有する
ものが好ましく、かつ、極性基としてはエステル基、エ
ーテル基、シアノ基、Ｎ−置換イミド等が好ましい。Preferably, such a polar polymer has a norbornene structural unit, and the polar group is preferably an ester group, an ether group, a cyano group, an N-substituted imide, or the like.
かかる共重合上ツマ−の具体例としては、５−メｌ〜キ
シカルボニルノルボルネン、５−（２−エチルへキシロ
キシ）カルボニル−５−メチルノルボルネン、５−フエ
ニロキシメチルノルボルネン。Specific examples of such copolymerizable materials include 5-mel-oxycarbonylnorbornene, 5-(2-ethylhexyloxy)carbonyl-5-methylnorbornene, and 5-phenyloxymethylnorbornene.
５−シアノノルボルネン、６−ジアツー１．４，５．８
−ジメタノ−１、４，４ａ、 ５．６．７．８．８ａ−
オクタヒドロナフタレン、Ｎ−ブチルナデイック酸イミ
ド等をあげることができる。5-cyanonorbornene, 6-diatu 1.4, 5.8
-dimethano-1,4,4a, 5.6.7.8.8a-
Examples include octahydronaphthalene and N-butylnadic acid imide.
上述した如き、メタセシス重合性モノマーは、メタセシ
ス重合触媒を不活性化する如き不純物が極力少ないもの
であることが要求される。As mentioned above, the metathesis polymerizable monomer is required to contain as few impurities as possible that would inactivate the metathesis polymerization catalyst.
本発明で用いるメタセシス重合触媒系における主触媒成
分としてはタングステン、レニウム、タンタル、モリブ
デン等のハライドなどの塩類が用いられるが、タングス
テン及びモリブデンの化合物が好ましく特にタングステ
ン化合物が好ましい。As the main catalyst component in the metathesis polymerization catalyst system used in the present invention, salts such as halides such as tungsten, rhenium, tantalum, and molybdenum are used, and compounds of tungsten and molybdenum are preferred, and tungsten compounds are particularly preferred.
かかるタングステン化合物としては、タングステンハラ
イド、タングステンオキシハライドなどが好ましく、よ
り具体的には、タングステンへキナクロライド、タング
ステンオキシクロライドなどが好ましい。また、有機ア
ンモニウムタングステン酸塩などが用いることができる
。かかるタングステン塩化合物は、直接上ツマ−に添加
すると、ただちにカチオン重合を開始することが判って
おり好ましくない。従ってタングステン塩化合物は不活
性溶媒例えばベンゼン、トルエン、クロロベンゼンなど
に予め懸濁し、少量のアルコール系化合物またはフェノ
ール系化合物を添加することによって可溶化させて使用
するのが好ましい。As such a tungsten compound, tungsten halide, tungsten oxyhalide, etc. are preferable, and more specifically, tungsten toquinachloride, tungsten oxychloride, etc. are preferable. Furthermore, organic ammonium tungstate and the like can be used. Such tungsten salt compounds are known to immediately start cationic polymerization when added directly to the upper layer, which is not preferred. Therefore, it is preferable to use the tungsten salt compound by suspending it in advance in an inert solvent such as benzene, toluene, chlorobenzene, etc., and solubilizing it by adding a small amount of an alcoholic compound or phenolic compound.
ざらに、上述した如き、好ましくない重合を予防するた
めにタングステン化合物１モルに対し、約１〜５モルの
ルイス塩基又はキレート化剤を添加することが好ましい
。かかる添加剤としてはアセチルアセトン、アセト酢酸
アルキルエステル類。Generally speaking, it is preferable to add about 1 to 5 moles of Lewis base or chelating agent to 1 mole of the tungsten compound in order to prevent undesirable polymerization as described above. Such additives include acetylacetone and acetoacetic acid alkyl esters.
テトラヒドロフラン、ベンゾニトリルなどをめげること
ができる。Tetrahydrofuran, benzonitrile, etc. can be used.
かくして、触媒成分を含むモノマー溶液（溶液Ａ）は、
実用上充分な安定性を有することになる。Thus, the monomer solution containing the catalyst component (solution A) is
It has sufficient stability for practical use.
一方メタセシス重合触媒系における活性他剤成分は、周
期律表第■〜第■族の金属のアルキル化物を中心とする
有機金属化合物、特にテトラアルキルスズ、アルキルア
ルミニウム化合物、アルキルアルミニウムハライド化合
物が好ましく、具体的には、塩化ジエチルアルミニウム
、ジ塩化エチルアルミニウム、１〜リオクチルアルミニ
ウム、ジオクチルアルミニウムアイオダイド、テトラブ
チル錫などを必げることかできる。これら活性化剤成分
としての有機金属化合物を、原料単量体に溶解すること
により、もう一方の溶液（溶液Ｂと呼ぶ）が形成される
。On the other hand, the active component in the metathesis polymerization catalyst system is preferably an organometallic compound mainly consisting of alkylated products of metals from Groups 1 to 2 of the periodic table, particularly tetraalkyl tin, alkyl aluminum compounds, and alkyl aluminum halide compounds. Specifically, diethylaluminum chloride, ethylaluminum dichloride, mono-lioctylaluminium, dioctylaluminum iodide, tetrabutyltin, etc. can be included. The other solution (referred to as solution B) is formed by dissolving these organometallic compounds as activator components in the raw material monomers.
前述の如く、かかる溶液中にエポキシシラン系シランカ
ップリング剤を添加して、重合と同時にガラス補強材処
理も同時におこなう方法をとることもできるが、同様に
前述の如き理由によってシラン処理を予めおこなったガ
ラス補強材を用いる方が好ましい。As mentioned above, it is also possible to add an epoxysilane-based silane coupling agent to such a solution and simultaneously perform glass reinforcing material treatment at the same time as polymerization, but it is also possible to perform silane treatment in advance for the same reason as described above. It is preferable to use a reinforced glass reinforcement.
本発明においては、基本的に前記溶液Ａ及び溶液Ｂを混
合することによって、架橋重合体成形物を得ることがで
きるが、上記組成のままでは、重合反応が非常に速く開
始されるので、成形用鋳型に充分流れ込まない間に硬化
が起こることがおり、度々問題となる場合が多く、前）
ホの如くそのために活性調節剤を用いることが好ましい
。In the present invention, a crosslinked polymer molded article can basically be obtained by mixing the solution A and solution B, but if the above composition remains unchanged, the polymerization reaction will start very quickly, so the molding Hardening may occur before it flows sufficiently into the casting mold, which is often a problem (see above).
For this purpose, it is preferable to use an activity regulator as shown in (e).
かかる調節剤としては、ルイス塩基類が一般に用いられ
、就中エーテル類、エステル類、ニトリル類などが用い
られる。具体例としては安息香酸エチル、ブチルエーテ
ル、ジグライムなどをあげることかできる。かかる調節
剤は両液は加えることができるが一般的に、有機金属化
合物の活性化剤の成分の溶液の側に添加した方が効果が
大きい場合がある。前述と同様にルイスペース基を有す
る七ツマ−を使用する場合には、それに調節剤の役目を
かねさせることができる。As such regulators, Lewis bases are generally used, among which ethers, esters, nitriles, etc. are used. Specific examples include ethyl benzoate, butyl ether, and diglyme. Such a regulator can be added to both solutions, but generally the effect may be greater when added to the solution of the organometallic compound activator component. When a heptamer having a Lewis space group is used as described above, it can also serve as a regulator.
メタセシス重合触媒系の使用量は例えば触媒成分として
タングステン化合物を用いる場合は、上記原料単量体に
対するタングステン化合物の比率は、モル基準で、約１
０００対１〜１５０００対１、好ましくは２０００対１
の付近でありまた、活性止剤成分はアルキルアルミニウ
ム類を用いる場合には、上記原料単量体に対するアルミ
ニウム化合物の比率はモル基準で約１００対１〜約２０
００対１、好ましくは約２００対１〜約５００対１の付
近が用いられる。The amount of the metathesis polymerization catalyst system used is, for example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the raw material monomer is about 1 on a molar basis.
000:1 to 15000:1, preferably 2000:1
In addition, when an alkyl aluminum is used as the activator component, the ratio of the aluminum compound to the raw material monomer is about 100:1 to about 20 on a molar basis.
00:1, preferably around 200:1 to about 500:1.
更に上述した如き、マスク剤や調節剤については、実験
によって上記触媒系の使用量に応じて、適宜、調節して
用いることができる。Further, as described above, the masking agent and the regulating agent can be appropriately adjusted and used depending on the amount of the catalyst system to be used through experiments.
本発明による架橋重合体成型物には、実用に当って、そ
の特性を改良または維持するために、さらに各種添加剤
を配合することができる。かかる添加剤としては、充填
剤、顔料、酸化防止剤、光安定剤、難燃化剤、高分子改
良剤などがある。このような添加剤においても本発明に
おけるガラス補強材と同じく架橋重合体が成形されて後
は添加することが不可能であるから、添加する場合には
予め前記した原料溶液に添加しておく必要がある。In practical use, various additives may be added to the crosslinked polymer molded product of the present invention in order to improve or maintain its properties. Such additives include fillers, pigments, antioxidants, light stabilizers, flame retardants, polymer modifiers, and the like. Similar to the glass reinforcing material in the present invention, it is impossible to add such additives after the crosslinked polymer is formed, so if they are added, they must be added to the raw material solution described above in advance. There is.
その最も容易な方法としては、前記溶液Ａおよび溶液Ｂ
のいずれか又は両方に前もって添加しておく方法をあげ
ることができるが、その場合、その液中の反応性の強い
触媒成分や、活性止剤成分と実用上ざしつかえある程度
には反応せず、かつ重合を阻害しないものでなくてはな
らない。どうしても、その反応がさけえないが共存して
も、重合は実質的に阻害しないものの場合は、単量体と
混合して、第三液を調整し、集合直前に、混合使用する
こともできる。The easiest method is to use the solution A and solution B.
One method is to add it to either or both of them in advance, but in that case, it does not react with the highly reactive catalyst component or deactivator component in the liquid to a certain extent for practical purposes. In addition, it must not inhibit polymerization. If the reaction cannot be avoided, but coexistence does not substantially inhibit polymerization, it can be mixed with the monomer to prepare a third liquid and mixed and used immediately before assembly. .
ガラス補強材以外の補強材又は充填剤をさらに必要に応
じて用いることもできる。かかるものとして例えば、雲
母、ウオラストナイトなどをあげることができるがこれ
らも、同様にエポキシシラン系シランカップリング剤に
よって表面処理したものを用いるのが好ましい。Reinforcing materials or fillers other than the glass reinforcing material can also be used as required. Examples of such materials include mica and wollastonite, but it is preferable to use those that have been surface-treated with an epoxysilane-based silane coupling agent.
また、本発明の架橋重合体成型物は、酸化防止剤を添加
しておくことが好ましく、そのためフェノール系又はア
ミン系の酸化防止剤を予め溶液中に加えておくことが望
ましい。これら順化防止剤の具体例としては、２．６−
ｔ−ブチル−Ｐ−クレゾール、Ｎ、Ｎ’−ジフェニル−
Ｐ−フェニレンジアミン、テトラキス［メチレン（３，
５−ジ−ｔ−ブチルー４−ヒドロキシシンナメ−１・）
］メタンなどがあげられる。Further, it is preferable to add an antioxidant to the crosslinked polymer molded product of the present invention, and therefore it is desirable to add a phenol-based or amine-based antioxidant to the solution in advance. Specific examples of these acclimatization inhibitors include 2.6-
t-Butyl-P-cresol, N,N'-diphenyl-
P-phenylenediamine, tetrakis[methylene (3,
5-di-t-butyl-4-hydroxycinname-1.)
] Examples include methane.
また、本発明による重合体成形物は、他の重合体を単量
体溶液状態の特に添加しておくことができる。かかる重
合体添加剤としてはエラストマの添加が成型物の耐衝撃
性を強めること及び溶液の粘度を調節する上で効果があ
るのは前述の如くである。かかる目的に用いられるエラ
ストマーとしては、スチレン−ブタジェンゴム、スチレ
ンブタジェン−スチレントップロックゴム、スチレンー
イソプレンースチレントップロツクゴム、ポリブタジェ
ン、ポリイソプレン、ブチルゴム、エチレンプロピレン
−ジェンターポリマー、二ｉ〜リルゴムなど広範なエラ
ストマーをあげることができる。また本発明の成型物に
おいて残留モノマが多く残ると特有の奥が発せられるこ
とがおる。Furthermore, other polymers, especially in the form of monomer solutions, can be added to the polymer molded article according to the present invention. As described above, the addition of an elastomer as such a polymer additive is effective in increasing the impact resistance of the molded product and controlling the viscosity of the solution. A wide variety of elastomers are used for this purpose, including styrene-butadiene rubber, styrene-butadiene-styrene toplock rubber, styrene-isoprene-styrene toplock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene-propylene-genterpolymer, di-lyl rubber, etc. elastomers can be used. Furthermore, if a large amount of residual monomer remains in the molded product of the present invention, a unique depth may be produced.
かかる残留モノマー減少剤としてα、α、α−トリクロ
ル１〜ルエン、トリクロル酢酸エステル、フタル酸クロ
ライド、安息香酸無水物、オキシ塩化リン、ベンゼンス
ルホン酸クロライド等を挙げることができる。Examples of such residual monomer reducing agents include α,α,α-trichloro1-toluene, trichloroacetic acid ester, phthalic acid chloride, benzoic anhydride, phosphorus oxychloride, benzenesulfonic acid chloride, and the like.
本発明の重合体成型物は、前記した如く、重合と成型と
を同時に行うことによって製造される。The polymer molded product of the present invention is produced by simultaneously performing polymerization and molding, as described above.
かかる成型法としては前述の如く、触媒と原料単遷体と
をスタテックミキ１ナー等の簡単なミキサーで混合する
か、前もって混合したプレミックスを型の中に流入せし
めるレジンインジェクション方式、触媒系を二つに分け
た溶液Ａと溶液Ｂをヘッド部で衝突混合せしめてそのま
ま型に流し込むＲＩＭ方式を採用することができる。特
にＲＩＭ方式か一般に用いられる。As mentioned above, such molding methods include mixing the catalyst and the raw material single transition material in a simple mixer such as a static mixer, a resin injection method in which a pre-mixed premix is flowed into a mold, and a method in which the catalyst system is mixed in two ways. It is possible to adopt the RIM method, in which solution A and solution B, which have been separated into two, are collided and mixed in a head section and poured into a mold as they are. In particular, the RIM method is commonly used.
いずれの場合も鋳型（モールド）への注入圧力は比較的
低圧であることができ、従って安価な鋳型を使用するこ
とか可能である。また、型内の重合反応が開始されると
反応熱によって型内の温度は急速に上昇し、短時間に重
合反応が終了する。In either case, the injection pressure into the mold can be relatively low, making it possible to use inexpensive molds. Further, when the polymerization reaction inside the mold starts, the temperature inside the mold rapidly rises due to the reaction heat, and the polymerization reaction ends in a short time.
ポリウレタン−ＲＩＭの場合と異なり、モールドから離
脱は容易であり、特別の離型剤を必要としない場合が多
い。Unlike polyurethane-RIMs, they are easy to release from the mold and often do not require special mold release agents.
ガラス補強材の適用は前述の如く、繊維形態の場合は予
め型内に充填しておく方法がとられ、粉末状の場合には
反応性溶液ＡおよびＢの少なくとも一方に分散しておき
それを型内に注入する方法がとられる。各々の利害得失
および留意すべき点については前述した通りでおる。As mentioned above, the glass reinforcing material is applied by filling it in a mold in advance if it is in the form of fibers, or by dispersing it in at least one of reactive solutions A and B if it is in powder form. A method of injecting into a mold is used. The advantages and disadvantages of each and points to keep in mind are as described above.
かかるガラス補強材の補強効果は、本発明によるエポキ
シシラン系シランカップリング剤の適切なる使用により
良好な接着が実現されたことにより、一般に補強材の添
加量に比例して改善される物性が多くなる。従って、そ
の用途より要求される物性に応じて添加量を定めればよ
い。一般により高い剛性が望まれる場合、より高いガラ
ス添加量が必要となるが、ガラス添加口が多くなるにつ
れて、繊維の場合は反応性溶液が空隙をつくることなく
、単繊維間に充分浸透するのが難しくなり、粉末の場合
は、粉末が懸濁された反応液の流動性が難しくなり、自
ら技術的な限界が生じることになる。ただ、かかる限界
は同じ繊維であってもその単繊維の寸法、集合体の形態
等によって異なり、その面での最適化も良好な補強体を
得るために必要である。The reinforcing effect of such a glass reinforcing material is generally improved in many physical properties in proportion to the amount of reinforcing material added because good adhesion is achieved through the appropriate use of the epoxysilane-based silane coupling agent according to the present invention. Become. Therefore, the amount to be added may be determined depending on the physical properties required by the application. Generally, if higher stiffness is desired, a higher amount of glass is required, but as the number of glass addition ports increases, in the case of fibers, the reactive solution can sufficiently penetrate between the single fibers without creating voids. In the case of powder, the fluidity of the reaction solution in which the powder is suspended becomes difficult, and this poses its own technical limitations. However, even if the fibers are the same, such limits vary depending on the dimensions of the single fibers, the form of the aggregate, etc., and optimization in this respect is also necessary to obtain a good reinforcing body.
一般に、ガラス補強材の充填率は、体積分率で０．０３
〜０．５、より好ましくは０．０５〜０．４の範囲が一
般に用いられる。Generally, the filling rate of glass reinforcement is 0.03 in terms of volume fraction.
A range of ˜0.5, more preferably 0.05-0.4 is generally used.
なお、かかるガラス補強材の適用にあたって成型物中に
均一に分布する必要はなく、要求性能をより満足せしめ
る最適配置を考えればよいことになる。粉末補強材で反
応液に分散して用いる場合は、特別の方法を用いなけれ
ば、かかる補強材を目的に応じて偏在さけることは難し
いが、ガラス繊維集合体を型内に配置する方式の場合は
、それを容易に実施することができる。In addition, when applying such a glass reinforcing material, it is not necessary to distribute it uniformly in the molded product, but it is sufficient to consider the optimum arrangement that better satisfies the required performance. When using a powdered reinforcing material dispersed in a reaction solution, it is difficult to avoid uneven distribution of such reinforcing material depending on the purpose without using a special method, but in the case of a method in which glass fiber aggregates are placed in a mold. can easily implement it.
例えば、同一成型物中の特定の部分の剛性等をあげたい
場合、その対応する場所にのみ、あるいはその部分によ
り高い充填率で、繊維集合体補強材を布置すればよいこ
とになる。また、板状物の曲げ剛性を重点に高くしたい
場合、両面近い場所により高い充填率で補強材をおくよ
うにすればよい。一方、表面が凹凸の少ないスムースな
表面が要求される場合、表面の部分にのみ、補強効果を
多少犠牲にしても、ファインデニールのガラス繊維をか
らみ合Ｖたガラスベールと呼ばれる集合体をおく方法を
とることもできる。For example, if you want to increase the rigidity of a specific part of the same molded product, you can place the fiber aggregate reinforcing material only in that corresponding location or at a higher filling rate in that part. In addition, when it is desired to increase the bending rigidity of a plate-shaped object, reinforcing materials may be placed at a higher filling rate near both sides. On the other hand, if a smooth surface with few irregularities is required, an aggregate called a glass veil made of intertwined fine denier glass fibers is placed only on the surface, even if the reinforcing effect is sacrificed to some extent. You can also take
また、かかる補強材の使用によって強度的に余裕が出来
た部分を、フオーム状物を充填することによって、曲げ
強度を維持しながら、軽量化する等の方法の適用も可能
となる。In addition, by filling the portion with a foam-like material that has an extra strength due to the use of such a reinforcing material, it is possible to reduce the weight while maintaining the bending strength.
ｄ１発明の効果
かくして得られたガラス補強重合体成型物は、改良され
た機械及び熱特性を有しており、従来のメタセシス重合
体成型物よりも、高い剛性２寸法安定性、熱変形温度等
の要求される用途に好適に用いることができる。即ち、
自動車、オートバイ。d1 Effect of the invention The thus obtained glass-reinforced polymer molding has improved mechanical and thermal properties, such as higher rigidity, two-dimensional stability, heat distortion temperature, etc. than conventional metathesis polymer moldings. It can be suitably used for applications requiring. That is,
cars, motorcycles.
ボート、スノー・モービル等の陸上、水上、各種運１１
ＲＢＮ器の部材、ゴルフ・カート、トラクター等の産業
用、レジャー用、スポーツ用、自走機器。Land, water, and various transportation such as boats, snowmobiles, etc. 11
RBN equipment parts, golf carts, tractors, and other industrial, leisure, sports, and self-propelled equipment.
移動機器類の部材、電曙、電子２機械類のハウジング等
、広範な用途に用いることができる。It can be used in a wide range of applications, such as parts for mobile equipment, housings for electric and electronic machinery, etc.
ｅ、実施例
以下に実施例をあげて本発明を説明する。実施例は説明
のためてあってそれに限定されるものではない。e. Examples The present invention will be explained with reference to Examples below. The examples are provided for illustrative purposes only and are not intended to be limiting.
［主触媒濃縮液の調製コ
高純度六塩化タングステン１９．８０（１（０，０５モ
ル）を乾燥トルエン９０７に窒素気流下で添加し、１−
ブタノール０．９２５ｇを５ｄの１〜ルエンに溶解した
ものを加え１時間攪拌し、次いでノニルフェノール１１
．０５ｇ（０，０５モル）及び１〜ル工ン５ｍｌよりな
る溶液を添加し１時間窒素パージ下にｍ拌する。１０ｇ
のアセチルアセトンを混合物に加え、副生ずる塩化水素
ガスを追い出しながら窒素パージ下に一晩攪拌を継続し
、その後、一部留出したトルエンを補い０６５Ｈタング
ステン含有触媒濃縮液を調整した。[Preparation of main catalyst concentrate: 19.80 (1 (0.05 mol)) of high-purity tungsten hexachloride was added to 907% of dry toluene under a nitrogen stream, and 1-
A solution of 0.925 g of butanol in 5 d of 1 to toluene was added, stirred for 1 hour, and then nonylphenol 11
．． A solution consisting of 0.5 g (0.05 mol) and 5 ml of 1 to 100 ml was added and stirred for 1 hour under a nitrogen purge. 10g
of acetylacetone was added to the mixture, stirring was continued overnight under a nitrogen purge while purging by-produced hydrogen chloride gas, and then some of the toluene distilled off was supplemented to prepare a 065H tungsten-containing catalyst concentrate.
［活性止剤濃縮液の調製］
ジ−ｎ−オクチルアルミニウムアイオダイド５．７０（
Ｊ 、 トリーローオクチルアルミニウム３１．１７
（］。[Preparation of active inhibitor concentrate] D-n-octyl aluminum iodide 5.70 (
J, tri-low octyl aluminum 31.17
(].
ジグライム１３．４２ｇを窒素気流下で混合し、次いで
ＤＣＰを添加し全体で１００７になるように希釈し１．
０）１アルミニウム含有活性化剤濃縮液を得た。13.42 g of diglyme was mixed under a nitrogen stream, and then DCP was added to dilute the total amount to 1.
0) 1 An aluminum-containing activator concentrate was obtained.
［シランカップリング剤］
表１に示す如き、本発明に包含されるエポキシシランと
比較のために他の一般的な市販シランカップリング剤を
用いてその効果の比較をおこなった。[Silane Coupling Agent] As shown in Table 1, the effects of the epoxy silane included in the present invention and other commercially available silane coupling agents were compared for comparison.
なあ、ガラス補強材処理のため使用した媒体を同表に併
記した。シランカップリング剤は、かかる媒体中に溶解
及び／又は分散状態で処理に用いられる。かかる処理に
用いる場合シランカップリング剤は媒体に対し１重量％
の濃度にした。Incidentally, the medium used for glass reinforcement treatment is also listed in the same table. The silane coupling agent is used in the treatment in a dissolved and/or dispersed state in such a medium. When used in such treatment, the silane coupling agent is 1% by weight based on the medium.
The concentration was set to
表
実施例１
［各シラン・カップリング剤のメタセシス重合阻害性及
び接着性テストコ
ジャー型ガラス容器の内面を、前記衣１のシランカップ
リング剤の媒体溶液で処理し、１２０°Ｃ１１０分間熱
処理して、内面が各々のシランカップリング剤で処理さ
れたガラス容器を調製した。Table Example 1 [Metathesis polymerization inhibition and adhesion test of each silane coupling agent The inner surface of a codger-type glass container was treated with a medium solution of the silane coupling agent of Clothing 1, and heat-treated at 120°C for 110 minutes. Glass containers whose inner surfaces were treated with each silane coupling agent were prepared.
一方、前記、主触媒濃縮液及び活性止剤濃縮液の各々を
ＤＣＰ９６．５ ｗｔ％、エチリデンノルボルネン３．
５ｗｔ％の七ツマー混合物に添加してタングステン含ｆ
ｆ１０．００１ Ｍの反応性溶液Ａ及びアルミニウム分
０．００３ Ｍの反応性溶液Ｂを調製した。On the other hand, each of the main catalyst concentrate and the deactivator concentrate was mixed with DCP of 96.5 wt% and ethylidene norbornene of 3.5 wt%.
5wt% of tungsten-containing F
A reactive solution A with f10.001 M and a reactive solution B with an aluminum content of 0.003 M were prepared.
かかる溶液Ａ、Ｂの各々１０ｍ１を別のシリンジに取り
出し３０’Ｃにした後、上記処理ガラス容器内に窒素気
流下、急速攪拌下に、両方を同時に押出し、二液の混合
を終わった時点で、攪拌機をあげ、がわりに熱電対を押
入し、両液のシリンジからの注入が終った時点から１０
０’Ｃに到達した時間（重合時間）を測定した。After taking out 10 ml of each of these solutions A and B into separate syringes and bringing the temperature to 30'C, both were simultaneously extruded into the above-mentioned processing glass container under nitrogen flow and rapid stirring, and when the mixing of the two liquids was completed, , raise the stirrer, insert a thermocouple in its place, and wait 10 minutes from the time when both liquids have been injected from the syringe.
The time taken to reach 0'C (polymerization time) was measured.
結果を表２に示す。かかる重合時間を比較することによ
り、シランカップリング剤のメタセシス重合に与える影
響が判ることになるが、（Ａ）のエポキシシランは重合
性に与える影響が小ざいことが判る。さらに生じた重合
体固体がシラン処理したガラス容器とよく密着したか、
簡単に離れたかを観測した。その結果を同様に表２に併
記した。The results are shown in Table 2. By comparing these polymerization times, the influence of the silane coupling agent on metathesis polymerization can be seen, and it can be seen that the epoxy silane (A) has a small influence on polymerizability. Furthermore, whether the resulting polymer solid adhered well to the silane-treated glass container or not.
I observed whether it left easily. The results are also listed in Table 2.
それで判る通りエポキシシランのみが、成型物がシラン
処理したガラス容器によく密着し、なかなか離れなかっ
た。他は重合の際の収縮もあって、ガラス容器から離れ
たり容易に離れるようになってあり、定性的ではめるが
エポキシシラン処理ガラスがメタセシス重合体と良好な
接着性を示すことが確認された。As can be seen, only with epoxy silane, the molded product adhered well to the silane-treated glass container and did not easily separate. Others were detached or easily detached from the glass container due to shrinkage during polymerization, confirming that the epoxysilane-treated glass exhibits good adhesion to the metathesis polymer, although qualitatively speaking. .
表
実施例２
［ガラス熾布入コンポジット・強度ナス１〜１バーニン
グ処理をして紡糸油剤等を揮散させ表面をきれいにした
ガラス織布（目付２１５ｇ／ｍ、平織厚ざ０．２２ｍｍ
）を表１の各シランカップリング剤溶液に浸漬、引き上
げてローラでしぼり、１日間風乾した後、熱風炉中で１
２０ ’Ｃ，１０分熱処理した。Table Example 2 [Glass woven composite with strength: 1 to 1] Glass woven fabric subjected to burning treatment to volatilize spinning oil and clean the surface (Weight: 215 g/m, plain weave thickness: 0.22 mm)
) was immersed in each silane coupling agent solution in Table 1, pulled out and squeezed with a roller, air-dried for 1 day, and then soaked in a hot air oven for 1 day.
Heat treatment was performed at 20'C for 10 minutes.
このように処理したガラス織布１０枚を、厚さ３．５ｍ
ｍたてよこ３０ＣｍＸ ３０Ｃｍの平板状の成型鋳型内
に重ねておき、その型内に実施例１と同じモノマー組成
にＦｉｒｅｓｔｏｎｅ社１ｓ８１？ −３ｔｅｒｏｎ
７２０を２里場％溶解したものに、主触媒濃縮液、活性
他剤濃縮液の各々を同様に溶解しタングステン含量０．
００１ Ｍにした反応性溶液Ａ及びアルミニウム含量０
．００３ Ｍの濃度にした反応性溶液Ｂを調製し、これ
を実用型のＲＩＭ成型機を用いて衝突混合注入しガラス
繊維含有率（Ｖｏｌ−含量）２２％のガラス織布強化メ
タセシス重合体成型板を１ｑた。10 pieces of glass woven fabric treated in this way were made into a 3.5m thick
30 cm x 30 cm vertically and horizontally in a flat molding mold, and in that mold, the same monomer composition as in Example 1 was added to Firestone's 1s81? -3teron
The main catalyst concentrate and other active agent concentrates were similarly dissolved in a 2% solution of 720 to obtain a tungsten content of 0.720.
Reactive solution A made to 0.001 M and aluminum content 0
．． A reactive solution B with a concentration of 0.003 M was prepared, and this was impingement-mixed and injected using a practical RIM molding machine to form a glass woven fabric reinforced metathesis polymer molded plate with a glass fiber content (Vol-content) of 22%. 1 q.
かかる成型板から、常法に従いナンプルを切り出して、
曲げ強度２曲げモジュラスを測定した。From this molded plate, cut out the numbers according to the usual method,
Bending strength and bending modulus were measured.
その結果を表３に示す。エポキシシランで処理したガラ
ス織布を用いたコンポジット板が、他のシランカップリ
ング剤で処理した織布を用いたコンボジノ１〜板や、シ
ラン処理なしの織布を用いたコンポジット板に比し、よ
り高い曲げ強度９曲げモジュラスを示していることが判
る。かかる曲げ強度１曲げモジュラスは、ガラス繊維強
化樹脂材の場合、ガラス繊維と樹脂との接着性の良否が
最も鋭敏に影響する性質とされておりエポキシシランが
良好な接着性を与えることを示している。The results are shown in Table 3. Composite plates using woven glass fabric treated with epoxy silane are compared to composite plates using woven fabrics treated with other silane coupling agents and composite plates using woven fabrics without silane treatment. It can be seen that it exhibits a higher bending strength and bending modulus. In the case of glass fiber-reinforced resin materials, the bending strength 1 bending modulus is said to be the property most sensitively affected by the quality of the adhesion between the glass fiber and the resin, and this shows that epoxy silane provides good adhesion. There is.
ざらに、不適当なシランカップリング剤を用いるとむし
ろ無処理の場合よりも悪い曲げ強度１曲げモジュラスし
か得られないことが判る。In general, it can be seen that when an inappropriate silane coupling agent is used, a bending strength of only 1 bending modulus is obtained which is worse than the case without treatment.
Claims (2)
たガラス補強材と、少なくとも１種のメタセシス重合性
シクロオレフィンをメタセシス重合触媒系によって重合
と成型を同時におこなって得られる重合体とより少なく
ともなるガラス強化重合体成型物。(1) Glass reinforcement made of at least a glass reinforcing material treated with an epoxysilane-based silane coupling agent and a polymer obtained by simultaneously polymerizing and molding at least one metathesis polymerizable cycloolefin using a metathesis polymerization catalyst system. Polymer molding.
１種を、エポキシシラン系シランカップリング剤で処理
したガラス補強材の存在下、メタセシス重合触媒系によ
って重合と成型を同時におこなうことを特徴とするガラ
ス強化重合体成型物の製造方法。(2) A glass-reinforced polymer characterized in that polymerization and molding of at least one metathesis-polymerizable cycloolefin are simultaneously performed using a metathesis polymerization catalyst system in the presence of a glass reinforcing material treated with an epoxysilane-based silane coupling agent. A method for manufacturing a composite molded product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15672988A JPH026525A (en) | 1988-06-27 | 1988-06-27 | Glass-reinforced polymer molding and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15672988A JPH026525A (en) | 1988-06-27 | 1988-06-27 | Glass-reinforced polymer molding and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH026525A true JPH026525A (en) | 1990-01-10 |
Family
ID=15634055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15672988A Pending JPH026525A (en) | 1988-06-27 | 1988-06-27 | Glass-reinforced polymer molding and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH026525A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007058249A1 (en) * | 2005-11-18 | 2007-05-24 | Rimtec Corporation | Norbornene resin moldings and process for production thereof |
-
1988
- 1988-06-27 JP JP15672988A patent/JPH026525A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007058249A1 (en) * | 2005-11-18 | 2007-05-24 | Rimtec Corporation | Norbornene resin moldings and process for production thereof |
| JP5357428B2 (en) * | 2005-11-18 | 2013-12-04 | Ｒｉｍｔｅｃ株式会社 | Norbornene-based resin molded body and method for producing the same |
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